Method for producing alkyl poly(3-hydroxypropionate), alkyl poly(3-hydroxypropionate), and composition containing the same.

Abstract

The present invention provides a method for producing alkyl poly(3-hydroxypropionate), which includes a step of producing alkyl poly(3-hydroxypropionate) by condensation polymerization of alkyl-3-hydroxypropionate, wherein the alkyl-3-hydroxypropionate has 2 to 20 carbon atoms, as well as alkyl poly(3-hydroxypropionate) and a composition thereof.

Description

[Technical Field]

[0001] [Cross-reference of related applications] This application claims priority based on Korean Patent Application No. 10-2022-0183172 dated December 23, 2022, and all content disclosed in the said Korean Patent Application is incorporated herein by reference.

[0002] The present invention relates to a method for producing alkyl poly(3-hydroxypropionate), alkyl poly(3-hydroxypropionate), and compositions containing the same. [Background technology]

[0003] Poly(3-hydroxypropionate) is a biodegradable polymer that not only has resistance to breakage but also excellent mechanical properties, making it a noteworthy eco-material.

[0004] Poly(3-hydroxypropionate) is produced by condensation polymerization of the monomer 3-hydroxypropionic acid (3-HP), and the production method of 3-hydroxypropionic acid by microbial fermentation is gaining attention as an environmentally friendly bio-process.

[0005] However, when producing 3-hydroxypropionic acid by microbial fermentation, other by-products are also generated during the fermentation process, requiring various steps to separate and purify the 3-hydroxypropionic acid from the fermentation liquid. In particular, 3-hydroxypropionic acid exhibits high hydrophilicity and has high solubility and reactivity in water, making separation and purification difficult.

[0006] One example of a method for recovering 3-hydroxypropionic acid is to convert it to alkyl-3-hydroxypropionate and purify it; however, this process often requires additional steps, such as removing the alkyl group. [Overview of the Initiative] [Problems that the invention aims to solve]

[0007] The present invention provides a method for producing alkyl poly(3-hydroxypropionate) by condensation polymerization of alkyl-3-hydroxypropionate, the alkyl poly(3-hydroxypropionate) produced therefrom, and compositions containing the same. [Means for solving the problem]

[0008] According to one embodiment of the present invention, a method for producing alkyl poly(3-hydroxypropionate) is provided, comprising the step of condensing an alkyl-3-hydroxypropionate to produce an alkyl poly(3-hydroxypropionate) represented by the following chemical formula 1, wherein the alkyl-3-hydroxypropionate has 2 to 20 carbon atoms in the alkyl group.

[0009] According to another embodiment of the present invention, an alkyl poly(3-hydroxypropionate) represented by the following chemical formula 1 is provided.

[0010] According to yet another embodiment of the present invention, an alkyl poly(3-hydroxypropionate) composition is provided, comprising an alkyl poly(3-hydroxypropionate) represented by the following chemical formula 1 and an alcohol having 2 to 20 carbon atoms.

[0011] The following describes in more detail a method for producing alkyl poly(3-hydroxypropionate) according to specific embodiments of the invention, alkyl poly(3-hydroxypropionate), and compositions containing the same.

[0012] Furthermore, unless it is explicitly stated that the steps constituting a manufacturing method described herein are sequential or continuous, or there is another special class, the steps constituting a single manufacturing method and other steps are not constrained to the order described in the specification. Therefore, the order of the steps constituting a manufacturing method can be changed to the extent that is easily understood by those skilled in the art, and in this case, the resulting changes that are obvious to those skilled in the art are included within the scope of the present invention.

[0013] Unless otherwise specified throughout this specification, “contains” or “includes” means to include a certain component (or constituent) without any particular restriction and should not be construed as excluding the addition of other components (or constituents).

[0014] Furthermore, unless otherwise specified herein, the weight-average molecular weight and number-average molecular weight of alkyl poly(3-hydroxypropionate) and the like can be measured using gel permeation chromatography (GPC). Specifically, the polymer or copolymer is dissolved in chloroform to a concentration of 1 mg / ml, and 100 μl is injected into the GPC chamber, where GPC analysis is performed at 40°C. At this time, chloroform is used as the GPC moving bed, flowing at a rate of 1.0 mL / min, two Agilent Mixed-B columns are connected in series, and an RI Detector is used as the detector. The Mw value and the like are derived using a calibration curve formed with polystyrene standard specimens. Twelve polystyrene standard specimens were used with weight-average molecular weights of 162 g / mol, 580 g / mol, 1,180 g / mol, 4,870 g / mol, 9,310 g / mol, 17,120 g / mol, 75,050 g / mol, 200,500 g / mol, 448,500 g / mol, 10,690,000 g / mol, 3,022,000 g / mol, and 6,545,000 g / mol.

[0015] According to one embodiment of the present invention, it includes the step of polycondensing alkyl-3-hydroxypropionate to produce alkyl poly(3-hydroxypropionate) represented by the following chemical formula 1, wherein the alkyl-3-hydroxypropionate has an alkyl group with 2 to 20 carbon atoms, and a method for producing alkyl poly(3-hydroxypropionate) is provided.

[0016]

Chemical formula

[0017] The inventors have found that when polycondensing alkyl-3-hydroxypropionate to produce the alkyl poly(3-hydroxypropionate), an alcohol with a boiling point lower than water is generated as a polycondensation by-product, and the by-product can be efficiently removed. The finally produced alkyl poly(3-hydroxypropionate) has a carboxyl group (-COOH) capped with an alkyl group, a low acid value of the polymer, a low vinyl group content in the end groups, and an excellent yield in the final recovery. Based on these findings, the present invention has been completed.

[0018] The method for producing alkyl poly(3-hydroxypropionate) according to the above embodiment can polycondense the alkyl-3-hydroxypropionate to produce alkyl poly(3-hydroxypropionate) represented by the above chemical formula 1.

[0019] When the alkyl-3-hydroxypropionate is polycondensed to produce an alkyl poly(3-hydroxypropionate), alcohol is generated as a polycondensation by-product. Since such alcohol has a lower boiling point than water, it can be efficiently removed even at a low temperature, and the content of the finally generated by-products is small, so the water removal step associated with the production of conventional poly(3-hydroxypropionate) can be omitted.

[0020] Further, in the alkyl poly(3-hydroxypropionate), the carboxyl group at the terminal is substituted with an alkyl ester, and finally the carboxyl group at the terminal is capped, and the acid value can be lowered. Since the acid value of the alkyl poly(3-hydroxypropionate) is lowered, the storage stability of the polymer can be improved, and the possibility of side reactions occurring can be reduced. Conventionally, in order to control the acid value of the polymer, an additive for reducing the acid value was added, but the production method according to the above embodiment can lower the acid value without adding an additional additive, and can reduce the generation of by-products.

[0021] On the other hand, although the acid value of the alkyl poly(3-hydroxypropionate) may show other tendencies depending on the number average molecular weight, for example, when the number average molecular weight of the alkyl poly(3-hydroxypropionate) exceeds 3,000 g / mol, the lower the number average molecular weight, the higher the acid value may be.

[0022] However, even if the number average molecular weight of the alkyl poly(3-hydroxypropionate) produced by the production method according to the above embodiment exceeds 3,000 g / mol, the acid value may be as low as 300.0 meq / kg or less. For example, the alkyl poly(3-hydroxypropionate) having a number average molecular weight exceeding 3,000 g / mol and being 8,000 g / mol or less may have an acid value of 300.0 meq / kg or less, 1.0 meq / kg or more and 290.0 meq / kg or less, 10.0 meq / kg or more, 20.0 meq / kg or more, 30.0 meq / kg or more, 50.0 meq / kg or more, or 280.0 meq / kg or less, 270.0 meq / kg or less, 250.0 meq / kg or less, 230.0 meq / kg or less, or 210.0 meq / kg or less. Furthermore, the alkyl poly(3-hydroxypropionate) having a number average molecular weight of more than 8,000 g / mol and 30,000 g / mol or less may have an acid value of 150.0 meq / kg or less, or 1.0 meq / kg or more and 140.0 meq / kg or less, or 10.0 meq / kg or more, 20.0 meq / kg or more, or 145.0 meq / kg or less, 140.0 meq / kg or less, 135.0 meq / kg or less, or 130.0 meq / kg or less.

[0023] On the other hand, the alkyl poly(3-hydroxypropionate) having a number average molecular weight of 300 g / mol or more and 3,000 g / mol or less may have an acid value of 1.0 meq / kg or more and 333.0 meq / kg or less, 2.0 meq / kg or more, 3.0 meq / kg or more, or 300.0 meq / kg or less, 200.0 meq / kg or less, 100.0 meq / kg or less, 70.0 meq / kg or less, 50.0 meq / kg or less, 30.0 meq / kg or less, or 20.0 meq / kg or less.

[0024] Furthermore, the alkyl-3-hydroxypropionate may be produced by condensation polymerization of the alkyl-3-hydroxypropionate, so that the vinyl group content at the alkyl-3-hydroxypropionate terminus is 40 mol% or less. For example, the vinyl group content at the alkyl-3-hydroxypropionate terminus may be 30 mol% or less, 20 mol% or less, 15 mol% or less, 10 mol% or less, or 5 mol% or less, or 0.01 mol% or more, 0.02 mol% or more, 0.03 mol% or more, 0.04 mol% or more, or 0.05 mol% or more.

[0025] The terminal groups of the alkyl poly(3-hydroxypropionate) may include hydroxyl groups, carboxyl groups, vinyl groups, etc. However, since alkyl poly(3-hydroxypropionate) is produced by the condensation polymerization of the alkyl 3-hydroxypropionate, the possibility of vinyl groups being present at the terminal groups is low. Vinyl groups are generated as a side reaction during the polymerization of 3-hydroxypropionic acid to poly(3-hydroxypropionic acid), but they act as a factor that deviates from the equivalent ratio in condensation polymerization, where the equivalent ratio of each functional group (hydroxyl group, carboxyl group) is important, thereby inhibiting the reaction rate and making it difficult to obtain high molecular weight polymers. Furthermore, the presence of vinyl groups in alkyl poly(3-hydroxypropionate) can lead to problems in the normal chain extension of alkyl poly(3-hydroxypropionate) through additional modification. Therefore, the poly(3-hydroxypropionate) has the advantage of fundamentally reducing the aforementioned disadvantages because it has fewer vinyl groups at its terminal groups.

[0026] The content of the terminal groups of the aforementioned poly(3-hydroxypropionic acid) was determined using a Brooker 500MHz NMR model. 1 The ratio of vinyl groups to end groups can be calculated by measuring with 1H-NMR. For example, the polymer can be dissolved in d-CDCl3 at a concentration of 8 mg / ml and measured, and the ratio can be calculated using the following formula 1.

number

[0027] The alkyl-3-hydroxypropionate may have 2 to 20, 2 to 10, 2 to 8, or 2 to 6 carbon atoms in the alkyl group, and may be, for example, ethyl, n-propyl, isopropyl, n-butyl, or tert-butyl.

[0028] Further, the alkyl poly(3-hydroxypropionate) may be represented by the following chemical formula (1).

Chemical formula

[0029] R is an alkyl group that caps the carboxy group of poly(3-hydroxypropionate), and may be derived from the alkyl of alkyl-3-hydroxypropionate. For example, R may be a linear or branched alkyl group represented by C n H 2n+1 (where n is an integer from 2 to 20), a linear or branched alkyl group represented by C n H 2n+1 (where n is an integer from 2 to 10), or a linear or branched alkyl group represented by C n H 2n+1 (where n is an integer from 2 to 6), and specifically may be an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, or a tert-butyl group.

[0030] The above-mentioned m represents the number of repeating structures, and for example, m may be an integer of 10 or more, or an integer between 10 and 600.

[0031] The alkyl poly(3-hydroxypropionate) may have a weight-average molecular weight of 500 g / mol or more, 600 g / mol or more, 1,000 g / mol or more, 2,000 g / mol or more, 3,000 g / mol or more, or 5,000 g / mol or more, and may also be 100,000 g / mol or less, 80,000 g / mol or less, 70,000 g / mol or less, 60,000 g / mol or less, 50,000 g / mol or less, 25,000 g / mol or less, or 20,000 g / mol or less. If the weight-average molecular weight of the alkyl poly(3-hydroxypropionate) is excessively low, it may have low crystallinity, not exist in a solid state, be easily crushed, and have low strength. If the weight-average molecular weight is excessively high, it may have high viscosity and be difficult to process.

[0032] The alkyl poly(3-hydroxypropionate) may have a number average molecular weight of 300 g / mol or more, 400 g / mol or more, 500 g / mol or more, 1,000 g / mol or more, 2,000 g / mol or more, 3,000 g / mol or more, or 5,000 g / mol or more, and may be 30,000 g / mol or less, 25,000 g / mol or less, 20,000 g / mol or less, 15,000 g / mol or less, 10,000 g / mol or less, 9,000 g / mol or less, or 8,000 g / mol or less. If the number average molecular weight of the alkyl poly(3-hydroxypropionate) is excessively low, it may have low crystallinity and not exist in a solid state, making it easily crushed and resulting in low strength. If the number average molecular weight is excessively high, it may have high viscosity and be difficult to process.

[0033] Furthermore, the alkyl poly(3-hydroxypropionate) may have a number-average molecular weight distribution (Mw / Mn) of 1.0 to 35.0. More preferably, the poly(3-hydroxypropionic acid) according to the present invention may have a molecular weight distribution of 1.3 or more, 1.4 or more, 1.7 or more, 1.8 or more, or 2.0 or more, and 35.0 or less, 30.0 or less, 25.0 or less, 20.0 or less, 11.0 or less, 5.0 or less, 3.0 or less, or 2.5 or less.

[0034] The alkyl poly(3-hydroxypropionate) produced by the production method according to the above embodiment can be produced by a condensation polymerization reaction of alkyl-3-hydroxypropionate. Specifically, the polycondensation of alkyl-3-hydroxypropionate may be carried out at a temperature of 50°C to 250°C. Furthermore, the polycondensation may be carried out for a period of 6 hours to 30 hours.

[0035] For example, the condensation polymerization may be carried out at a temperature of 50°C or higher, or 70°C or higher, or 90°C or higher, or 110°C or higher, and 250°C or lower, or 230°C or lower, or 200°C or lower, for a period of 6 hours or higher, or 8 hours or higher, or 10 hours or higher, and 30 hours or lower, or 28 hours or lower, or 26 hours or lower. When carried out under these conditions, alkyl poly(3-hydroxypropionate) having the physical properties and weight-average molecular weight within the optimal range to be achieved in the present invention can be produced in excellent yield.

[0036] The aforementioned polymerization condensation may be carried out under the use of one or more catalysts selected from the group consisting of sulfonic acid catalysts, metal oxides, metal chlorides, and metal alkoxide catalysts.

[0037] The sulfonic acid-based catalysts are not limited to these, but include, for example, benzenesulfonic acid, n-butylbenzenesulfonic acid, n-octylbenzenesulfonic acid, n-dodecylbenzenesulfonic acid, pentadecylbenzenesulfonic acid, 2,5-dimethylbenzenesulfonic acid, 2,5-dibutylbenzenesulfonic acid, o-aminobenzenesulfonic acid, m-aminobenzenesulfonic acid, p-aminobenzenesulfonic acid, 3-amino-4-hydroxybenzenesulfonic acid, and 5-amino-2-methylbenzenesulfonic acid. Zensulfonic acid, 3,5-diamino-2,4,6-trimethylbenzenesulfonic acid, 2,4-dinitrobenzenesulfonic acid, p-chlorobenzenesulfonic acid, 2,5-dichlorobenzenesulfonic acid, hydroxynitrobenzenesulfonic acid, aminotoluenesulfonic acid, p-phenolsulfonic acid, aminophenolsulfonic acid, cumenesulfonic acid, xylenesulfonic acid, o-cresolsulfonic acid, m-cresolsulfonic acid, p-cresolsulfonic acid, p-toluenesulfonic acid (p-TSA ), methanesulfonic acid (m-SA), trifluoromethanesulfonic acid, nanofluorobutane-1-sulfonic acid, 2-naphthalenesulfonic acid, p-xylene-4-sulfonic acid, 2-toluenesulfonic acid, 3-toluenesulfonic acid, 2-ethylbenzenesulfonic acid, 3-ethylbenzenesulfonic acid, 4-ethylbenzenesulfonic acid, taurine, cyclopentanesulfonic acid, cyclohexanesulfonic acid, sulfuric acid, camphorsulfonic acid, etc. may also be used.

[0038] The aforementioned metal oxides are not limited to those mentioned above, but may also include germanium dioxide, zinc oxide, tin oxide, antimony trioxide, iron trioxide, aluminum trioxide, silicon dioxide, titanium dioxide, and others.

[0039] The aforementioned metal alkoxides are not limited to those mentioned above, but may include, for example, titanium butoxide, titanium isopropoxide, aluminum isopropoxide, yttrium isopropoxide, germanium ethoxide, silicon ethoxide, tin octanoate, and the like.

[0040] The aforementioned metal chlorides are not limited to those mentioned above, but may include, for example, potassium chloride, calcium chloride, nickel chloride, cobalt chloride, magnesium chloride, manganese chloride, iron chloride, barium chloride, zinc chloride, aluminum chloride, tin chloride, and the like.

[0041] The catalyst may be used in an amount of 0.001 mol% to 10 mol% relative to the alkyl-3-hydroxypropionate. For example, the catalyst may be used in an amount of 0.010 mol% or more, or 0.050 mol% or more, or 0.10 mol% or more, or 0.20 mol% or more relative to the alkyl-3-hydroxypropionate, and may be used in amounts of 10 mol% or less, 5 mol% or less, 3 mol% or less, or 1 mol% or less. If the catalyst is used in excessively small amounts, the polymerization activity may not be sufficient, and if the catalyst is used in excessively large amounts, the amount of residual catalyst will increase, leading to depolymerization such as transesterification reactions, which can cause decomposition of the polymer or a decrease in molecular weight.

[0042] Furthermore, the production method according to the above embodiment may include the steps of: melt polymerization of alkyl-3-hydroxypropionate to produce alkyl-3-hydroxypropionic acid oligomer (Step 1); and further polymerization of the alkyl-3-hydroxypropionic acid oligomer to produce alkyl poly(3-hydroxypropionate) (Step 2).

[0043] The aforementioned melt polymerization means that the reactant alkyl-3-hydroxypropionic acid and the product alkyl-3-hydroxypropionic acid oligomer remain in a liquid state. For this reason, in the present invention, the reaction temperature in step 1 is adjusted to a temperature of 40°C to 120°C. Although not theoretically limited, under the melt polymerization conditions described above, the formation of cyclic oligomers is suppressed during the polymerization of alkyl-3-hydroxypropionic acid. Preferably, the reaction temperature in step 1 is 40°C or higher, 45°C or higher, 50°C or higher, 55°C or higher, 60°C or higher, 65°C or higher, 70°C or higher, 75°C or higher, or 80°C or higher, and may also be 135°C or lower, 130°C or lower, 125°C or lower, 120°C or lower, 115°C or lower, 110°C or lower, 105°C or lower, 100°C or lower, or 95°C or lower.

[0044] Step 1 can be carried out at a pressure of 5 mbar to 200 mbar. When the reaction in Step 1 is carried out at such a low pressure, polymerization of alkyl-3-hydroxypropionic acid can be promoted. More preferably, Step 1 can be carried out at a pressure of 6 mbar or more, or 7 mbar or more, and at 190 mbar or less, 180 mbar or less, 170 mbar or less, 160 mbar or less, 150 mbar or less, 140 mbar or less, 130 mbar or less, 120 mbar or less, 110 mbar or less, 100 mbar or less, 90 mbar or less, 80 mbar or less, 70 mbar or less, 60 mbar or less, 50 mbar or less, 40 mbar or less, 30 mbar or less, 20 mbar or less, or 10 mbar or less.

[0045] The reaction time in step 1 can be appropriately adjusted considering the molecular weight and yield of the alkyl-3-hydroxypropionic acid oligomer produced, and is preferably carried out for 1 to 5 hours. Within this reaction time, the molecular weight of the alkyl-3-hydroxypropionic acid oligomer can be increased to an appropriate level, and the production yield can also be improved.

[0046] Furthermore, the catalyst may be added in a predetermined amount during the reaction in step 1. The catalyst promotes the polymerization of alkyl-3-hydroxypropionic acid and has the effect of suppressing the formation of cyclic oligomers during the polymerization process of alkyl-3-hydroxypropionic acid.

[0047] On the other hand, for the melt polymerization of step 1, a step of drying the alkyl-3-hydroxypropionic acid may be performed before step 1 if necessary. This drying removes the moisture present in the alkyl-3-hydroxypropionic acid. In this case, the drying temperature is preferably 40 to 95°C, the drying pressure is preferably 10 mbar to atmospheric pressure, and the drying time is preferably 1 to 10 hours.

[0048] In the case of step 2, the alkyl-3-hydroxypropionic acid oligomer can be further polymerized to produce alkyl poly(3-hydroxypropionate).

[0049] Unlike step 1, since the reactant is an oligomer, the polymerization temperature may be higher and the pressure lower compared to step 1. Preferably, the polymerization temperature in step 2 may be 50°C or higher, or 70°C or higher, or 90°C to 250°C, or 230°C or lower, 200°C or lower, 180°C or lower, or 160°C or lower.

[0050] The pressure in step 2 is 1 mbar or less, more preferably 0.9 mbar or less, 0.8 mbar or less, 0.7 mbar or less, 0.6 mbar or less, 0.5 mbar or less, 0.4 mbar or less, 0.3 mbar or less, 0.25 mbar or less, 0.20 mbar or less, 0.19 mbar or less, or 0.18 mbar or less, and is 0.01 mbar or more, 0.02 mbar or more, 0.03 mbar or more, 0.04 mbar or more, 0.05 mbar or more, 0.06 mbar or more, 0.07 mbar or more, 0.08 mbar or more, 0.09 mbar or more, or 0.01 mbar or more.

[0051] The reaction time in step 2 can be appropriately adjusted considering the molecular weight and yield of the alkyl poly(3-hydroxypropionate) produced, preferably for 6 hours or more, or 8 hours or more, or 10 hours or more, and 30 hours or less, or 28 hours or less, or 26 hours or less. Within the reaction time, the molecular weight of the alkyl poly(3-hydroxypropionate) can be increased to an appropriate level, and the production yield can also be improved.

[0052] On the other hand, since step 2 is carried out immediately after step 1, the catalyst added in step 1 will also participate in the reaction in step 2. Therefore, the catalyst described in step 1 can also be used in step 2.

[0053] Another embodiment of the present invention provides an alkyl poly(3-hydroxypropionate) represented by the following chemical formula 1. [ka] In the aforementioned chemical formula 1, R is C n H 2n+1 A linear or branched alkyl group represented by (n is an integer from 2 to 20), m is an integer greater than or equal to 10.

[0054] The alkyl poly(3-hydroxypropionate) may be produced by the alkyl poly(3-hydroxypropionate) production method according to the first embodiment.

[0055] Furthermore, the acid value, vinyl group content among the terminal groups, weight-average molecular weight, and number-average molecular weight of the alkyl poly(3-hydroxypropionate) are as described above.

[0056] Furthermore, according to yet another embodiment of the invention, an alkyl poly(3-hydroxypropionate) composition is provided, comprising an alkyl poly(3-hydroxypropionate) represented by the above chemical formula 1 and an alcohol having 2 to 20 carbon atoms.

[0057] The aforementioned composition may be produced by the alkyl poly(3-hydroxypropionate) production method according to the first embodiment.

[0058] The above manufacturing method involves condensation polymerization of alkyl-3-hydroxypropionate to produce poly(3-hydroxypropionate), which may generate an alcohol having 2 to 20 carbon atoms as a by-product. This alcohol has a lower boiling point than water and can be efficiently removed even at low temperatures. As a result, the amount of by-products generated is small, and the water removal step associated with conventional poly(3-hydroxypropionate) production can be omitted.

[0059] The alcohol may have 2 to 20, 2 to 10, 2 to 8, or 2 to 6 carbon atoms. For example, the alcohol may be ethanol, n-propanol, isopropanol, n-butanol, or tert-butanol. [Effects of the Invention]

[0060] The present invention provides a method for producing alkyl poly(3-hydroxypropionate) by condensation polymerization of alkyl-3-hydroxypropionate, which efficiently removes by-products such as alcohol, and ultimately provides alkyl poly(3-hydroxypropionate) and compositions containing it, which have a low acid value in the polymer produced and minimal formation of vinyl groups due to side reactions. [Modes for carrying out the invention]

[0061] The invention will be described in more detail by the following embodiments. However, the following embodiments are merely illustrative of the present invention, and the content of the present invention is not limited to the following embodiments. Experimental Example 1

[0062] Fifteen g of dehydrated ethyl-3-hydroxypropionate was placed in a reactor, and 0.4 mol% of octyltriamine relative to ethyl-3-hydroxypropionic acid was added as a catalyst. The reactor temperature and pressure were maintained at 90°C and 10 torr, respectively, and the reaction was carried out for 2 hours to produce ethyl-3-hydroxypropionate oligomer. Subsequently, the reactor temperature and pressure were adjusted to 90°C and 0.2 torr, respectively, and the reaction was carried out for 24 hours to produce ethyl poly(3-hydroxypropionate). Experimental Example 2

[0063] Ethyl poly(3-hydroxypropionate) was prepared in the same manner as in Experimental Example 1, except that p-TSA (p-Toluenesulfonic acid) was used instead of octyltriamine. Experimental Example 3

[0064] Ethyl poly(3-hydroxypropionate) was prepared in the same manner as in Experimental Example 1, except that tin chloride (SnCl2) was used instead of octyltriamine.

[0065] <Rating> 1. Measurement by gas chromatography (GC) The reaction products from Experimental Examples 1 to 3 were measured by gas chromatography (GC) to determine the content of by-products other than the final product, ethyl poly(3-hydroxypropionate), such as ethanol, ethyl-3-hydroxypropionate, dimer, and other by-products. The results are shown in Table 1 below. [Table 1]

[0066] According to Table 1 above, in Experimental Examples 2 and 3, the starting material ethyl-3-hydroxypropionate was measured at a low level of 64.5% by weight or less, while in Experimental Example 1, ethyl-3-hydroxypropionate was measured at 99.2% by weight, confirming that the polymerization condensation reactivity was lower compared to Experimental Examples 2 and 3.

[0067] Example 1 15 g of ethyl-3-hydroxypropionate, from which the water had been removed, was placed in a reactor, and 19.7 mg of m-SA (Methanesulfonic aicd) was added as a catalyst at a concentration of 0.2 mol% relative to the ethyl-3-hydroxypropionate. The reactor temperature and pressure were maintained at 90°C and 10 torr, respectively, and the reaction was carried out for 2 hours to produce ethyl-3-hydroxypropionate oligomer. Subsequently, the reactor temperature and pressure were adjusted to 90°C and 0.2 torr, respectively, and the reaction was carried out for 24 hours to produce ethyl poly(3-hydroxypropionate).

[0068] Example 2 15 g of dehydrated tert-butyl-3-hydroxypropionate was placed in a reactor, and 19.7 mg of m-SA (Methanesulfonic aicd) was added as a catalyst at a concentration of 0.2 mol% relative to the tert-butyl-3-hydroxypropionate. The reaction was carried out for 2 hours while maintaining the temperature and pressure in the reactor at 90°C and 10 torr, respectively, to produce ethyl-3-hydroxypropionate oligomer. Subsequently, the temperature and pressure in the reactor were adjusted to 90°C and 0.2 torr, respectively, and the reaction was carried out for 24 hours to produce tert-butyl poly(3-hydroxypropionate).

[0069] Example 3 Tert-butyl poly(3-hydroxypropionate) was prepared in the same manner as in Example 2, except that 39.4 mg (0.4 mol%) of m-SA (Methanesulfonic aicd) was used instead of 19.7 mg (0.2 mol%).

[0070] Example 4 Tert-butyl poly(3-hydroxypropionate) was prepared in the same manner as in Example 2, except that 63.3 mg (0.2 mol%) of p-TSA was used instead of 19.7 mg (0.2 mol%) of m-SA (Methanesulfonic aicd).

[0071] Example 5 Tert-butyl poly(3-hydroxypropionate) was prepared in the same manner as in Example 2, except that 126.6 mg (0.4 mol%) of p-TSA was used instead of 19.7 mg (0.2 mol%) of m-SA (Methanesulfonic aicd).

[0072] Example 6 Tert-butyl poly(3-hydroxypropionate) was produced in the same manner as in Example 5, except that the reaction temperature was controlled to 120°C in all cases.

[0073] Example 7 Tert-butyl poly(3-hydroxypropionate) was produced in the same manner as in Example 5, except that the reaction temperature was controlled to 140°C in all cases.

[0074] Example 8 Tert-butyl poly(3-hydroxypropionate) was produced in the same manner as in Example 5, except that the reaction temperature was controlled to 160°C in all cases.

[0075] Example 9 Tert-butyl poly(3-hydroxypropionate) was produced in the same manner as in Example 5, except that the reaction temperature was controlled to 180°C in all cases.

[0076] Example 10 15 g of dehydrated n-butyl-3-hydroxypropionate was placed in a reactor, and 126.6 mg of p-TSA was added as a catalyst at a concentration of 0.4 mol% relative to the n-butyl-3-hydroxypropionate. The reactor temperature and pressure were maintained at 90°C and 10 torr, respectively, and the reaction was carried out for 2 hours to produce n-butyl-3-hydroxypropionate oligomer. Subsequently, the reactor temperature and pressure were adjusted to 90°C and 0.2 torr, respectively, and the reaction was carried out for 24 hours to produce n-butyl poly(3-hydroxypropionate).

[0077] Example 11 Fifteen g of dehydrated n-butyl-3-hydroxypropionate was placed in a reactor, and 0.4 mol% titanium butoxide (Ti(BuO)4) was added as a catalyst relative to the n-butyl-3-hydroxypropionate. The reactor temperature and pressure were maintained at 90°C and 10 torr, respectively, and the reaction was carried out for 2 hours to produce n-butyl-3-hydroxypropionate oligomer. Subsequently, the reactor temperature and pressure were adjusted to 90°C and 0.2 torr, respectively, and the reaction was carried out for 24 hours to produce n-butyl poly(3-hydroxypropionate).

[0078] Example 12 n-butyl poly(3-hydroxypropionate) was produced in the same manner as in Example 11, except that the reaction conditions (90°C / 0.2 torr / 24 hours) were adjusted to 120°C and 0.2 torr and the reaction was controlled for 8 hours.

[0079] Example 13 n-butyl poly(3-hydroxypropionate) was produced in the same manner as in Example 11, except that the reaction conditions (90°C / 0.2 torr / 24 hours) were adjusted to 140°C and 0.2 torr and the reaction was controlled for 8 hours.

[0080] Example 14 n-butyl poly(3-hydroxypropionate) was produced in the same manner as in Example 11, except that the reaction conditions (90°C / 0.2 torr / 24 hours) were adjusted to 160°C and 0.2 torr and the reaction was controlled for 18 hours.

[0081] Example 15 n-butyl poly(3-hydroxypropionate) was produced in the same manner as in Example 11, except that the reaction conditions (90°C / 0.2 torr / 24 hours) were adjusted to 180°C and 0.2 torr and the reaction was controlled for 8 hours.

[0082] Comparative Example 1 Fifteen g of 3-hydroxypropionic acid, from which the water had been removed, was placed in a reactor, and 63.3 mg of p-TSA was added as a catalyst at a concentration of 0.2 mol% relative to the 3-hydroxypropionic acid. The reactor temperature and pressure were maintained at 90°C and 10 torr, respectively, and the reaction was carried out for 2 hours to produce a 3-hydroxypropionate oligomer. Subsequently, the reactor temperature and pressure were adjusted to 90°C and 0.2 torr, respectively, and the reaction was carried out for 24 hours to produce poly(3-hydroxypropionate).

[0083] Comparative Example 2 Poly(3-hydroxypropionate) was prepared in the same manner as in Comparative Example 1, except that 19.7 mg (0.2 mol%) of m-SA was used instead of 63.3 mg (0.2 mol%) of p-TSA.

[0084] Comparative Example 3 15 g of methyl-3-hydroxypropionate, from which the water had been removed, was placed in a reactor, and 19.7 mg of m-SA was added as a catalyst at a concentration of 0.2 mol% relative to the methyl-3-hydroxypropionate. The reaction was carried out for 2 hours while maintaining the temperature and pressure in the reactor at 90°C and 10 torr, respectively, to produce methyl-3-hydroxypropionate oligomer. Subsequently, the temperature and pressure in the reactor were adjusted to 90°C and 0.2 torr, respectively, and the reaction was carried out for 24 hours to produce methyl poly(3-hydroxypropionate).

[0085] <Evaluation> 1. Measurement by gel permeation chromatography For the polymers produced in the above Examples and Comparative Examples, the weight-average molecular weight, number-average molecular weight, and polydispersity index were measured by gel permeation chromatography (GPC: gel permeation chromatography, Waters Alliance e2695), and the results are shown in Table 2 below.

[0086] <GPC analysis conditions> After dissolving the product in chloroform to a concentration of 1 mg / ml, 100 μl was injected into GPC, and GPC analysis was performed at 40 °C. At this time, chloroform was used for the mobile phase of GPC, which flowed in at a flow rate of 1.0 mL / min. Two Agilent Mixed-B columns were connected in series and used, and an RI Detector was used as the detector. The Mw value was derived using a calibration curve formed with polystyrene standard specimens. The weight-average molecular weights of the polystyrene standard specimens were 162 g / mol, 580 g / mol, 1,180 g / mol, 4,870 g / mol, 9,310 g / mol, 17,120 g / mol, 75,050 g / mol, 200,500 g / mol, 448,500 g / mol, 10,690,000 g / mol, 3,022,000 g / mol, and 6,545,000 g / mol, a total of 12 types.

[0087] 2. Evaluation of yield For the polymers produced in the above Examples and Comparative Examples, the yield was calculated using the following Formulas 2 and 3, and the results are shown in Table 2 below. <Formula 2> Theoretical value = amount of alkyl-3-hydroxypropionate input (g) × (polymer molecular weight / alkyl-3-hydroxypropionate molecular weight) <Formula 3> Yield (%) = amount of finally produced polymer obtained / theoretical value × 100

[0088] 3. Analysis of vinyl group content of end groups The polymers produced in Examples 1 to 3, 11 and Comparative Examples 1 to 3 were subjected to a Baker 500 MHz NMR model. 1 The ratio of vinyl groups to total end groups was calculated by 1H-NMR measurement. Specifically, each polymer was dissolved in d-CDCl3 at a concentration of 8 mg / ml and measured. The ratio was calculated using Equation 1 below, and the results are shown in Table 3.

number

[0089] In the above formula 1, a is 6.3 ppm C=C 1 H is the area value, b is 3.8 ppm HO-CH2- 2 This is the area value of H. 4. Measurement of polymer acid value The acid value of the polymers produced in Examples 1 to 3, 11 and Comparative Examples 1 to 3 was measured according to ASTM D4662, and the results are shown in Table 4 below.

[0090] Specifically, a DGi 116-solvent electrode was used with a Mettler Toledo T5 system, and a 0.02N potassium methoxide solution was used as the titration solution. The titration point was then analyzed. [Table 2] [Table 3] [Table 4]

[0091] Referring to Table 2 above, it was confirmed that the polymers of the examples produced with ethyl-3-hydroxypropionate, tert-butyl-3-hydroxypropionate, or n-butyl-3-hydroxypropionate had significantly higher yields compared to the polymer of Comparative Example 3 produced with methyl-3-hydroxypropionate.

[0092] Furthermore, referring to Table 3, it was confirmed that the examples in which polymers were produced using alkyl-3-hydroxypropionate differed from Comparative Examples 1 and 2, in which polymers were produced using 3-hydroxypropionic acid, in that vinyl groups were not included among the end groups of the polymer.

[0093] Furthermore, referring to Table 4, we confirmed that while the acid value of polymers is affected by the number-average molecular weight, despite Comparative Example 1 and Example 3 having similar number-average molecular weights, the acid value of Example 3 was significantly lower than that of Comparative Example 1. We also confirmed that despite Example 1 and Comparative Example 3 having similar number-average molecular weights, the acid value of Example 1 was lower than that of Comparative Example 3.

Claims

1. The process includes the step of condensing an alkyl-3-hydroxypropionate to produce an alkyl poly(3-hydroxypropionate) represented by the following chemical formula 1; A method for producing alkyl poly(3-hydroxypropionate), 【Chemistry 1】 In the aforementioned chemical formula 1, R is an n-butyl group or a tert-butyl group. A method where m is an integer greater than or equal to 10.

2. The method for producing alkyl poly(3-hydroxypropionate) according to claim 1, wherein the condensation polymerization is carried out under the presence of one or more catalysts selected from the group consisting of sulfonic acid catalysts, metal oxides, metal chlorides, and metal alkoxide catalysts.

3. The method for producing alkyl poly(3-hydroxypropionate) according to claim 2, wherein the catalyst is used in an amount of 0.001 mol% or more and 10 mol% or less relative to the alkyl-3-hydroxypropionate.

4. The method for producing alkyl poly(3-hydroxypropionate) according to claim 1, wherein the polycondensation is carried out at a temperature of 50°C or higher and 250°C or lower.

5. The method for producing alkyl poly(3-hydroxypropionate) according to claim 1, wherein the polycondensation is carried out for a period of 6 hours or more and 30 hours or less.

6. The method for producing alkyl poly(3-hydroxypropionate) according to claim 1, wherein the alkyl poly(3-hydroxypropionate) has a weight-average molecular weight of 500 g / mol or more and 100,000 g / mol or less.

7. The method for producing alkyl poly(3-hydroxypropionate) according to claim 1, wherein the alkyl poly(3-hydroxypropionate) has a number average molecular weight of 300 g / mol or more and 30,000 g / mol or less.

8. The alkyl poly(3-hydroxypropionate) having a number average molecular weight of 300 g / mol or more and 3,000 g / mol or less has an acid value of 1.0 meq / kg or more and 333.0 meq / kg or less. The alkyl poly(3-hydroxypropionate) having a number average molecular weight greater than 3,000 g / mol and 8,000 g / mol or less has an acid value of 300.0 meq / kg or less. The method for producing alkylpoly(3-hydroxypropionate) according to claim 1, wherein the alkylpoly(3-hydroxypropionate) has a number average molecular weight greater than 8,000 g / mol and less than or equal to 30,000 g / mol, and has an acid value of 150.0 meq / kg or less.

9. The method for producing alkyl poly(3-hydroxypropionate) according to claim 1, wherein the alkyl poly(3-hydroxypropionate) has a content of 30 mol% or less of terminal vinyl groups.

10. The alkyl poly(3-hydroxypropionate) represented by the following chemical formula 1, 【Chemistry 2】 In the aforementioned chemical formula 1, R is an n-butyl group or a tert-butyl group. m is an integer greater than or equal to 10, and is an alkylpoly(3-hydroxypropionate).

11. The alkyl poly(3-hydroxypropionate) having a number average molecular weight of 300 g / mol or more and 3,000 g / mol or less has an acid value of 1.0 meq / kg or more and 333.0 meq / kg or less. The alkyl poly(3-hydroxypropionate) having a number average molecular weight greater than 3,000 g / mol and 8,000 g / mol or less has an acid value of 300.0 meq / kg or less. The alkyl poly(3-hydroxypropionate) according to claim 10, wherein the number average molecular weight is greater than 8,000 g / mol and less than or equal to 30,000 g / mol, and the acid value is 150.0 meq / kg or less.

12. The alkyl poly(3-hydroxypropionate) according to claim 10, wherein the content of terminal vinyl groups is 30 mol% or less.

13. The alkyl poly(3-hydroxypropionate) represented by the following chemical formula 1 and Alcohols containing 2 to 20 carbon atoms, Alkyl poly(3-hydroxypropionate) composition, 【Transformation 3】 In the aforementioned chemical formula 1, R is an n-butyl group or a tert-butyl group. A composition in which m is an integer greater than or equal to 10.

14. The alkyl poly(3-hydroxypropionate) having a number average molecular weight of 300 g / mol or more and 3,000 g / mol or less has an acid value of 1.0 meq / kg or more and 333.0 meq / kg or less. The alkyl poly(3-hydroxypropionate) having a number average molecular weight greater than 3,000 g / mol and 8,000 g / mol or less has an acid value of 300.0 meq / kg or less. The alkyl poly(3-hydroxypropionate) composition according to claim 13, wherein the alkyl poly(3-hydroxypropionate) has a number average molecular weight greater than 8,000 g / mol and less than or equal to 30,000 g / mol, and has an acid value of 150.0 meq / kg or less.

15. The alkyl poly(3-hydroxypropionate) composition according to claim 13, wherein the alkyl poly(3-hydroxypropionate) has a content of 30 mol% or less of terminal vinyl groups.

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